著者
長野 哲雄
出版者
The Society of Synthetic Organic Chemistry, Japan
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.47, no.9, pp.843-854, 1989-09-01 (Released:2010-01-22)
参考文献数
88
被引用文献数
6 9

The review describes about the compounds which can enhance the generation of superoxide (O2-) and hydrogen peroxide (H2O2) in the biological systems and about the novel metal complexes which can have superoxide dismutase activity in vivo. Some compounds are readily reduced by one or two electron (s) to produce their reduced forms. When these reduced forms can react with dioxygen, the compounds often have the potential to increase the production (s) of O2- and/or H2O2 in living cells. The review shows that hypervalent heteropentalenes, 3, 4-diaza-1, 6, 6 a-trithiapentalenes (TTP) and 1, 6-dioxa-6 a-thia-2, 5-diazapentalenes (HEP), are capable of this in studies with electrochemical reactions and Escherichia coli, respectively The hypervalent structures may be essential for enhancement of O2- and/or H2O2 generation in living cells. The review also shows that novel metal complexes, Fe (II) -tetrakis N, N, N'- (2-pyridylmethyl) ethylenediamine (Fe-TPEN) and Fe (III) -tris [N- (2-pyridylmethyl) -2-aminoethyl] amine (Fe-TPAA) act as potent superoxide dismutase mimics in vivo. The iron complexes appear to have the possibility of being applied therapeutically.
著者
伊藤 英人 松岡 和 矢野 裕太 柴田 万織 伊丹 健一郎
出版者
公益社団法人 有機合成化学協会
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.78, no.7, pp.671-682, 2020-07-01 (Released:2020-07-09)
参考文献数
63
被引用文献数
1 1

Polycyclic aromatic compounds are recognized as highly important class of compounds in materials science due to their high utility as organic semiconductors and organic optoelectronic materials. In general, they can be obtained through the established π-extension methods from unfunctionalized aromatics, while the syntheses are often suffered from multi-step process including halogenation, coupling reaction, Diels-Alder reaction, aromatization and so on. Recently, we have established a novel synthetic concept “annulative π-extension (APEX)” which has the potential to have a tremendous impact on the fields of synthetic chemistry since it allows rapid access to fused aromatic systems from simple unfunctionalized aromatic compounds in a single step. Here we report our recent results of palladium-catalyzed APEX reactions for the synthesis of polycyclic aromatic hydrocarbons, polycyclic heteroaromatics, nanographenes and even graphene nanoribbons from readily available unfunctionalized aromatics.
著者
大和 武彦
出版者
The Society of Synthetic Organic Chemistry, Japan
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.53, no.6, pp.487-499, 1995-06-01 (Released:2009-11-16)
参考文献数
67
被引用文献数
15 17

The catalytic applications of Nafion-H, a superacidic perfluororesinsulfonic acid in organic synthesis are reviewed. Nafion-H, the acid form of a commercial Nafion-K ionomer, is a highly acidic (H0≥-12) solid catalyst superior to conventional resinsulfonic acids such as sulfonated polystyrenes in its catalytic activity, thermal stability and chemical resistance.Nafion-H catalyst is effective in a wide range of liquid and gas phase reactions, including electrophilic substitutions on aromatic nuclei, dehydration of alcohols, rearrangements, polymerizations and so on. Nafion-H and related perfluoroalkanesulfonic acids are not only much stronger acids but are also stable in corrosive environments and at temperature up to 210°C. Furthermore, specific advantages of using insoluble resins as catalysts include i) ease of by-product separation from the main reaction product usually by simple filtration; ii) prevention of intermolecular reaction of reactive species or functional groups by simulating high dilution conditions; iii) the possibility of reusing recovered reagents as well as eliminating the use of volatile or noxious substances.
著者
関根 康平
出版者
公益社団法人 有機合成化学協会
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.80, no.6, pp.595-596, 2022-06-01 (Released:2022-06-09)
参考文献数
10

Dehydrogenative silylation, which produces vinyl silanes, was generally regarded as a side reaction in hydrosilylation of alkenes. However, due to a utility of vinyl silanes, transition-metal catalyzed dehydrogenative silylations have been developed. This mini-review focuses on recent developments of manganese-catalyzed selective dehydrogenative silylation of alkenes.
著者
川本 拓治 上村 明男
出版者
公益社団法人 有機合成化学協会
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.80, no.6, pp.554-562, 2022-06-01 (Released:2022-06-09)
参考文献数
28

Vinyl triflates are valuable precursors for vinyl cations, vinyl carbenes, and electrophiles for transition-metal-catalyzed cross-coupling reactions. However, in these reactions, the trifluoromethyl group is not installed in the final products. The radical reactions of vinyl triflates were limited until our beginning. We initially achieved the synthesis of α-trifluoromethylated ketones from vinyl triflates using triethyl borane as a radical initiator. Since the reaction proceeds chemoselectivity toward the conjugated vinyl triflates, we achieved the chemo- and regio-selective trifluoromethylation of 1,3-bis(vinyl triflates). We developed one-pot trifluoromethylation from aryl alkynes with perfluoroalkanesulfonic acids in the presence of AIBN as a radical initiator. In addition, a crossover experiment and DFT calculations support that the reaction proceeds through an intermolecular pathway. The radical reaction of vinyl triflates in the presence of alkenes afforded γ-trifluoromethylated ketones. We also developed a one-pot triflation-trifluoromethylation-triflation of imines leading trifluoromethyl-substituted vinyl trifluoromethanesulfonic amides.
著者
上村 明男
出版者
公益社団法人 有機合成化学協会
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.80, no.6, pp.541-553, 2022-06-01 (Released:2022-06-09)
参考文献数
130

Plastics are indispensable material that supports our daily life. The amounts of their production and waste are increasing in every year, and their recycling is recognized as a key issue for sustainable development of the world. Plastics are carbon resources and should be recycled in a proper manner. Chemical recycling is a concept in which plastics are treated chemically to give monomer or related compounds that would serve further use. Although chemical recycling of plastics is an ideal way, it is still difficult to carry it out. In this account, we focus on the depolymerization reaction of several plastics, and show how basic knowledge and recent development of synthetic organic chemistry provide important idea and solution on this matter. Use of supercritical alcohols and ionic liquids offered new and valuable methods. We applied the methodology developed here to biomass conversion, and we show the results about this application.
著者
井上 重治 瀬崎 正次
出版者
The Society of Synthetic Organic Chemistry, Japan
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.51, no.4, pp.327-349, 1993-04-01 (Released:2009-11-16)
参考文献数
189
被引用文献数
6 6

Recently, opportunistic fungal infections are becoming more important in the compromised patients.The review summarizes current attempts to find new and useful antifungal antibiotics mainly active against opportunistic fungal pathogens. Based on the chemical structures, antifungal antibiotics reported since 1987 are conveniently classified into 12 types : 1) polyene macrolide and related antibiotics, 2) lipopeptide antibiotics, 3) glycolipid antibiotics, 4) glycolipid/lipopeptide related antibiotics, 5) alkylphenol antibiotics, 6) terpenoid antibiotics, 7) cyclodepsipeptide antibiotics, 8) peptidonucleoside antibiotics, 9) amino acid antibiotics, 10) condensed polycyclic aromatic antibiotics, 11) halogenopyrrole antibiotics and 12) miscellaneous antibiotics. Finally, the principles and strategy for screening of antifungal antibiotics are discussed.
著者
北村 充
出版者
公益社団法人 有機合成化学協会
雑誌
有機合成化学協会誌 (ISSN:00379980)
巻号頁・発行日
vol.72, no.1, pp.14-25, 2014-01-01 (Released:2014-03-04)
参考文献数
87
被引用文献数
8 13

2-Azido-1,3-dimethylimidazolinium chloride (ADMC) and its corresponding hexafluorophosphate (ADMP) were found to be safe and efficient diazo-transfer reagents to various organic compounds. ADMC was prepared by the reaction of 2-chloro-1,3-dimethylimidazolinium chloride (DMC) and sodium azide. ADMP was isolated as a crystal having thermal stability and low explosibility. ADMC and ADMP reacted with 1,3-dicarbonyl compounds under mild basic conditions to give 2-diazo-1,3-dicarbonyl compounds in high yields, which are easily isolated because the by-products are highly soluble in water. Naphthols also reacted with ADMC to give corresponding diazonaphthoquinones in good to high yields. Furthermore, ADMP shows efficient diazo-transfer ability to primary amines even without the aid of a metal salt such as Cu(II). Using this diazotization approach, various alkyl/aryl azides were obtained directly from corresponding primary amines in high yields. In addition, ADMC/ADMP could be used as azide-transfer and amidation reagents.